CN109283163A - Method based on calcium-metal-organic framework materials as fluorescence probe detection L-cysteine - Google Patents
Method based on calcium-metal-organic framework materials as fluorescence probe detection L-cysteine Download PDFInfo
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- CN109283163A CN109283163A CN201811137853.4A CN201811137853A CN109283163A CN 109283163 A CN109283163 A CN 109283163A CN 201811137853 A CN201811137853 A CN 201811137853A CN 109283163 A CN109283163 A CN 109283163A
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a kind of methods based on calcium-metal-organic framework materials as fluorescence probe detection L-cysteine.Realized as quencher to the fluorescent quenching of Ca-MOFs complex first with lead chloride, then adding L-cysteine realizes the fluorescence recovery effects to Quenching System, thus indirectly in measurement system L-cysteine content.The fluorescence probe Ca-MOFs complex that the present invention uses is that a kind of good water solubility, chemical stability be high, the much lower hole coordination polymer material of toxicity, is based on Ca (NO3)2·4H2O is as inorganic ions node, and rigidity symmetrical (1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid) prepares synthesis using easy " one kettle way " solvent heat technological means as organic bridge ligand, and chemical general formula is { [Ca1.5(HL1)(DMF)2]·DMF}.The present invention also discloses the preparation process for being applied to the detection and analysis work and Ca-MOFs complex crystal material of L-cysteine using metal-organic framework materials as fluorescence probe simultaneously.
Description
Technical field
The invention belongs to the preparation synthesis of metal-organic framework materials and fluorescence sense fields, and in particular to one kind is based on low
Toxic metal organic framework material is as fluorescence probe using the side of the highly selective detection L-cysteine of fluorescence " on/off " mode
Method.
Background technique
L-cysteine is a kind of indispensable amino acid in human body, active containing sulfydryl as a kind of important biomolecule
Compound, vital role is play in biological cell function.L-cysteine helps to maintain intracellular oxygen
Change reduction activation, protein synthesis, removing toxic substances, metabolism, the physiological activities such as Cellular Signaling Transduction Mediated and gene regulation.It is also
A kind of biological identification substance of potential neurotoxin either medical diagnosis on disease, it is closely bound up with the Physiological effect of human body mechanism.
And the content of L-cysteine will have a direct impact on the normal physiological activity of organism in vivo, when half Guang ammonia of L- in human body
It includes that trichochromes are reduced that the deficiency of acid content, which can induce various disease symptoms, and hemochrome is reduced, skin injury, liver damage
Wound, drowsiness, the forfeiture of muscle and fat.Therefore, most important is become for the measurement of L-cysteine content in organism, closely
Cause huge concern over a little years.The quantitative analysis of L-cysteine is detected at present, usually utilizes some traditional analysis skills
Art means, such as high performance liquid chromatography, Capillary Electrophoresis, electrochemical analysis method, mass spectral analysis and colorimetric method etc..However,
These traditional analytical technology means are low etc. there are detection process complexity, detection time length, poor anti jamming capability, detection sensitivity
Disadvantage.Therefore, aobvious based on a kind of quantitative detection that fast and simple, efficient and sensible analysis method is applied to L-cysteine is developed
It obtains particularly important.
In recent years, metal-organic framework materials (MOFs) are because having diversified topological structure and special functional character in science
Research field is widely paid close attention to.It is using inorganic metal ion or metal cluster as node and multiple tooth organic bridge ligand
It is basic structural unit by being self-assembly of a kind of novel hybrid inorganic-organic porous coordination polymer material, due in
The functional qualitative diversity of heart metal ion and organic bridge ligand creates MOFs and shows more novel specially property,
Such as it is all with huge specific surface area, functional cellular structure, controllable surface texture properties, good chemical stability etc.
More good characteristics.More importantly the MOFs structure of different functionalities can be designed according to demand, by metal ion
With the special sex modification of the purpose of organic ligand selection and MOFs surfaces externally and internally structure, thus reach to MOFs material structure with
The Effective Regulation of property.Due to the various complicated structure and special functional character of MOFs, in gas storage, absorption and divide
It is with a wide range of applications from, fields such as bio-imaging, heterogeneous catalysis, drug delivery and chemical sensitisation.Based on MOFs structure
Hole track on middle organic ligand in organic active connection site rich in and metal ion, causes guest molecule to exist
Specific recognition can be carried out inside the duct MOFs or on surface, causes the influence to MOFs material fluorescence intensity, thus MOFs
Material can be used as fluorescence probe applied to optochemical sensor.With some traditional luminescent material quantum dots, up-conversion, gold
Belong to nanoparticle to compare with shell-nuclear compounded material, the central metallic ions of MOFs material and organic bridge ligand can provide fluorescence
Emission sites, so that it has in terms of selective enumeration method inorganic zwitterion, object biomolecule and nitroaromatic
Unique advantage.But about metal-organic framework materials as fluorescence probe using the detection life of fluorescence " on/off " mode selective
There are no relevant reports so far containing quantifier elimination for L-cysteine in object liquid.
Summary of the invention
The object of the present invention is to provide a kind of good water solubility, chemical stability is high, exempt from special sex modification, hypotoxicity
Detection method of the metal-organic framework materials to biomolecule L-cysteine.Using easy " one kettle way " solvent thermal technology hand
A kind of good low toxic metal organic framework material of fluorescence property of Duan Hecheng designs a kind of fluorescence " on/off " mould as fluorescence probe
Formula realizes detection fast and simple to L-cysteine, highly selective, highly sensitive.
Technical purpose of the invention is achieved through the following technical solutions:
A method of L-cysteine being detected as fluorescence probe based on calcium-metal-organic framework materials, which is characterized in that is pressed
It is carried out according to following steps:
(1) preparation of Standard Stock solutions: the metal-organic framework materials that quality is 0.0060 g are weighed and are dissolved in 60 mL deionizations
It is shaken up in water and is allowed to be completely dissolved；Weighing quality is that 0.7780 g trihydroxy aminomethane-hydrochloric acid (Tris-HCl) is dissolved in 50 mL
Deionized water in shake up and be allowed to be completely dissolved；It weighs 0.0178 g lead chloride analytical reagent and is dissolved in 8 mL deionized waters and shake up
It is allowed to be completely dissolved；It weighs 0.0078 g L-cysteine and is dissolved in shaking up in 8 mL deionized waters and be allowed to be completely dissolved；
(2) aaerosol solution (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), standard Tris-HCl
Buffer solution (pH=7.2,0.1 M) and 100 μ L standard chlorination lead solutions (1.6 mM) are settled to 4 mL with deionized water, mix
Conjunction uniformly stands lead to be chlorinated and metal-organic framework materials interaction reaches stable state, and MOFs material is caused to generate fluorescence
Signal is quenched, detection architecture is in fluorescence intensity positioned at the fluorescence closed state compared with low background, utilizes sepectrophotofluorometer
Record fluorescence emission spectrum；
(3) solution to be measured containing L-cysteine is added into the detection architecture solution of step (2), uniformly mixing, which is stood, makes L-
After cysteine and lead chloride interaction are stablized, detection architecture is set to be restored in the fluorescence intensity compared with low background, benefit
Fluorescence emission spectrum is recorded with sepectrophotofluorometer；Pass through the changing value of fluorescence emission spectral intensity recorded twice and fitting
Linear equation guidance obtain the concentration of L-cysteine in solution to be measured.
The linear equation of the fitting be △ I=14.199C+29.32,0.25-40 μM of the range of linearity, minimum detectability 91
NM, R2Value is 0.98043.
The method of detection L-cysteine of the present invention, it is characterised in that metal-organic framework materials be it is a kind of based on (1,
1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid)-Ca (NO3)2Hypotoxicity porous coordination polymer material, the material is brilliant
Body structure belongs to monoclinic system, C2/cSpace group, chemical general formula are as follows: { [Ca1.5(HL1)(DMF)2] DMF, with Ca2+As
Central metallic ions, HL is (1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid) as organic bridge ligand, organic
Ligand structure are as follows:
More detailed description of the present invention is as follows:
The present invention uses fluorescence " on/off " mode detection L-cysteine using metal-organic framework materials as fluorescence probe
Method, which is characterized in that carry out in accordance with the following steps:
(1) preparation of standard solution
100 mg L-1Metal-organic framework materials solution: weigh 0.0060 g metal-organic framework materials be dissolved in 60 mL go from
In sub- water, it is allowed to form uniform suspension using 5 min of ultrasonic cleaner ultrasonic disperse.
The Tris-HCl buffer of 0.1 M: it weighs 0.7880 g trishydroxymethylaminomethane-hydrochloric acid and is dissolved in 40 mL deionized waters
In, it is 7.4 that NaOH solution (0.5 M), which is then constantly added dropwise, and is adjusted to pH using pH meter, is finally settled to 50 with deionized water
mL。
8 mM chlorination lead solutions: it weighs 0.0178 g lead chloride analytical reagent and is dissolved in shaking up in 8 mL deionized waters and be allowed to complete
Dissolution.
8 mM L-cysteine solution: it weighs 0.0078 g L-cysteine and is dissolved in 8 mL deionized waters, and as mother
Liquid is configured to a series of standard solution of various concentrations.
(2) aaerosol solution (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), standard Tris-HCl
Buffer solution (0.1 M) and 100 μ L standard chlorination lead solutions (1.6 mM) are settled to 4 mL with deionized water, are uniformly mixed quiet
It sets lead to be chlorinated and metal-organic framework materials interaction reaches stable state, MOFs material is caused to generate fluorescent quenching letter
Number, detection architecture is in fluorescence intensity positioned at the fluorescence closed state compared with low background, is recorded using sepectrophotofluorometer glimmering
Optical emission spectroscopy.
(3) a series of L-cysteine standard solution that various concentrations are added into the detection solution system of step 1 is uniformly mixed
It stands, interacts to L-cysteine and lead chloride, so that the fluorescence intensity being quenched is restored and detects recovery
Fluorescence emission spectrum, linear pass can be fitted by the changing value of emission spectrum fluorescence intensity and the concentration of L-cysteine
It is equation.
(4) the detection application based on metal-organic framework materials to L-cysteine, which is characterized in that half Guang of L- in reaction system
Good linear relationship is presented in the concentration of propylhomoserin and the changing value of fluorescent emission intensity, and linear equation is △ I=14.199C+
29.32,0.25-40 μM of the range of linearity, minimum detectability 91 nM, R2Value is 0.98043.
(5) when being applied to the detection of L-cysteine using metal-organic framework materials, to the detection solution system of step (2)
Middle addition is containing L-cysteine solution to be measured, after uniformly mixing standing stablizes L-cysteine and lead chloride interaction,
So that detection architecture is restored in the fluorescence intensity compared with low background, sepectrophotofluorometer is utilized to record fluorescence emission
Spectrum.L- in solution to be measured is calculated by the changing value of fluorescence emission spectral intensity and the linear equation of fitting that record twice
The concentration of cysteine.
Metal-organic framework materials are based on (1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid)-Ca in the present invention
(NO3)2Complex, using calcium nitrate tetrahydrate inorganic salts as inorganic node, the symmetrical terphenyl-tetrabasic carboxylic acid conduct of rigidity
Organic bridge ligand, one kettle way solvent thermal technology have synthesized a kind of porous coordination polymer material with three-dimensional structure.Wherein
The structure of organic ligand are as follows:
The crystal structure of metal-organic framework materials in the present invention belongs to monoclinic system, C2/cSpace group.Using graphite monochromator
Mo-KαRadiation (λ=0.71073) diffraction light sources are used as, are usedScanning mode collects point diffraction, and crystal structure uses
SHELXS-97 and SHELXL-97 program is solved with direct method, and is corrected using complete matrix least square method.Detailed crystallography
Data are as shown in the table:
The crystallographic data table of 1 metal-organic framework materials of table
The crystal of complex belongs to monoclinic system, C in the present invention2/cThe basic structural unit of space group, complex contains 1.5
CaIICentral ion (Ca2With 0.5 Ca1), the HL of a deprotonation1 3-, two coordination DMF molecules and a free lattice DMF
Molecule.Ca1 and HL1 3-6 O atoms (O1, O1A, O5A, O5B, O8A, O8B) be coordinated, Ca2 and HL1 3-5 carboxyl oxygens
((O9 is mutually coordinated the oxygen atom for two DMF molecules that O2, O5A, O6A, O7A and O8A) and end are coordinated atom with O10).Wherein
Ca1, Ca2 are connected to form the Ca of three cores by carboxylic acid atom with Ca2A3O4Cluster is as second level component (SBUS).Each HL1 3-Match
Body makes three carboxylic acid groups connect three neighbouring three core Ca with multiple tooth bridge modeIISecond level component, being finally built into has two dimension
The porous coordination frame 1 of structure.The part bond distance of metal-organic framework materials 1 and bond angle data, as shown in the table:
The part bond distance of 2 metal-organic framework materials of table and bond angle tables of data
Method disclosed by the invention based on calcium-metal-organic framework materials as fluorescence probe detection L-cysteine is had
Have the active effect that
(1) the invention discloses being synthesized based on " one kettle way " solvent thermal technology, a kind of new type water-solubility is good, fluorescence property is good, chemical
The metal-organic framework materials that stability is high, toxicity is low have good biocompatibility, and do not need complicated specificity
Modification and functionalization can be used as detection of the fluorescence probe applied to L-cysteine content in organism.
(2) fluorescence probe material MOFs used in the present invention is that the novel hypotoxicity porous coordination polymer material of one kind has
Good biocompatibility applies it well in field of biological detection.Metal-organic framework materials it is good water-soluble
Property, solve the difficulty detected in organic solvent system using MOFs as probe material in current most of document reports
Topic, so that its application range is more extensive.
(3) a kind of fluorescence " on/off " mode system is designed the present invention is based on metal-organic framework materials be applied to L-cysteine
Detection, have many advantages, such as selectivity good, high sensitivity, strong antijamming capability.It can be realized using this method simple and efficient, high
Effect delicately detects, and the detection range of linearity is 0.25-40 μM, and detection is limited to 91 nM.
(4) long traditional detection method bring detection time, detection process complexity, height can be effectively avoided to disappear using this method
Consumption, poor anti jamming capability, the disadvantages of sensitivity is low, detection limit is lower, are perplexed.By the present invention with previous detection method such as colorimetric method,
Chromatography, electrochemical process method compare, with the obvious advantage as shown in the table:
The method that table 3 detects L-cysteine compares
Detailed description of the invention
Fig. 1 is the chemical formula structure schematic diagram that metal-organic framework materials are used in the present invention；
Fig. 2 is the powder diffraction XRD spectra that metal-organic framework materials are used in the present invention；
Fig. 3 is the uv absorption spectra and fluorescence emission spectrogram of compound that metal-organic framework materials are used in the present invention；
Fig. 4 be various concentration metal organic framework complex material fluorescence intensity and respectively add same concentrations lead chloride it is sudden
Go out efficiency curve diagram；
Fig. 5 is fluorescent quenching chronergy figure of the lead chloride to metal organic framework complex material；
Fig. 6 is fluorescence recovery time of the L-cysteine to the mixed system of metal-organic framework materials and lead chloride solution composition
Effect picture；
Fig. 7 is that the lead chloride of various concentration restores relational graph to the fluorescence of metal organic framework complex material；
Fig. 8 is fluorescent quenching and fluorescence recovery curve figure of the different pH value to metal organic framework complex material；
Fig. 9 is in the present invention using metal organic framework complex material and lead chloride mixed solution system detection L-cysteine
Fluorescence spectra；
Figure 10 is in the present invention using metal organic framework complex material and lead chloride mixed solution system detection half Guang ammonia of L-
The Linear Fit Chart of acid；
Figure 11 is the Selective recognition histogram that metal-organic framework materials are applied to L-cysteine detection in the present invention.
Specific embodiment
Carry out the present invention is described in detail below by specific embodiment and Detailed description of the invention.Unless stated otherwise, of the invention
Used in technological means be method known in those skilled in the art.In addition, embodiment be interpreted as it is illustrative,
The range being not intended to limit the present invention, the spirit and scope of the invention are limited only by the claims that follow.For those skilled in the art
Member for, under the premise of without departing substantially from spirit and scope of the present invention, in these embodiments material component and dosage carry out
Various changes or change also belong to protection scope of the present invention.
Reagent C a (NO as used in the following examples3)2·4H2O, DMF, nitric acid, ether, ethyl alcohol, lead chloride are analysis
It is pure, it is purchased from lark prestige Reagent Company.(1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid) organic ligand is purchased from Beijing
Chemical Co., Ltd. of Hua Shengrui section.Required amino acid is purchased from Tianjin recovery fine chemistry industry research institute, is the examination of BR biochemistry
Agent, purity 99%.
Embodiment 1
Metal organic framework complex material prepares synthesis and structure characterization
(1) 141.6 mg Ca (NO are weighed3)2·4H2O and 42.1 mg (1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetracarboxylic acids
Acid) organic ligand reagent is evenly dispersed in 2 mL deionized waters and 6 mL DMF stirring 0.5-1 h, 3-7 μ L is then added
The HNO of (0.33 M)3Solution.Then mixed solution is transferred to the stainless steel autoclave with polytetrafluoroethylliner liner
In, 96-100 h is heated under the conditions of 120-140 DEG C of temperature.It is finally cooled to room temperature by 48-50 h, the production that will be obtained
Available colourless bulk crystals after object water and ether wash for several times.
(2) the metal-organic framework materials crystal prepared is based on H4L1Yield 37%.C31H32Ca1.5N3O11Elemental analysis reason
By value (%): C 54.54, H 4.73, N 6.15；Elemental analysis experiment value (%): C 54.79, H 4.96, N 6.15；Table
Element composition is substantially consistent with theoretical value in bright complex.
(3) structural characterization of metal-organic framework materials
Crystal structure determination uses 1000 CCD type X-ray single crystal diffractometer of BRUKER SMART, using graphite monochromator
Mo-KαRadiationλ=0.71073) diffraction light sources are used as, are usedScanning mode collects point diffraction, and crystal structure uses
SHELXS-97 and SHELXL-97 program is solved with direct method, and is corrected using complete matrix least square method.The organic bone of its metal
The XRD analogue data and experimental data of frame complex are as shown in Figure 1.Detailed crystallographic data is as shown in the table.
The crystallographic data table of 1 metal-organic framework materials of table
(4) the crystal structure description of metal-organic framework materials 1
The crystal of complex belongs to monoclinic system, C in the present invention2/cThe basic structural unit of space group, complex contains 1.5
CaIICentral ion (Ca2 and 0.5 Ca1), the HL of a deprotonation1 3-, two coordination DMF molecules and a free lattice DMF
Molecule.Ca1 and HL1 3-6 O atoms (O1, O1A, O5A, O5B, O8A, O8B) be coordinated, Ca2 and HL1 3-5 carboxyl oxygens
((O9 is mutually coordinated the oxygen atom for two DMF molecules that O2, O5A, O6A, O7A and O8A) and end are coordinated atom with O10).Wherein
Ca1, Ca2 are connected to form the Ca of three cores by carboxylic acid atom with Ca2A3O4Cluster is as second level component (SBUS).Each HL1 3-Match
Body makes three carboxylic acid groups connect three neighbouring three core Ca with multiple tooth bridge modeIISecond level component, finally constructs two-dimensional structure
Nanoporous be coordinated frame 1, as shown in Figure 2.The part bond distance of metal-organic framework materials 1 and bond angle data, such as following table institute
Show:
The part bond distance of 2 metal-organic framework materials of table and bond angle tables of data
Embodiment 2
Series of standards stock solution is prepared, to test to subsequent experimental
(1) 100 mg L-1The metal-organic framework materials suspension preparation of concentration: weighing quality is that 0.0060 g metal is organic
Framework material is dissolved in 60 mL deionized waters, is allowed to form uniform suspension using 5 min of ultrasonic cleaner ultrasonic disperse
It is stand-by to place shady place for liquid.
The preparation of the Tris-HCl buffer of (2) 0.1 M: weighing quality is that 0.7880 g trishydroxymethylaminomethane-hydrochloric acid is molten
It is shaken up in 40 mL deionized waters and is allowed to be completely dissolved, NaOH solution (0.5 M) constantly then is added dropwise, adjusting pH using pH meter is
7.2,50 mL finally are settled to deionized water, are put in refrigerator stand-by.
(3) 8 mM chlorination lead solutions are prepared: being accurately weighed 0.0178 g lead chloride analytical reagent and are dissolved in 8 mL deionized waters and shake
It is even to be allowed to be completely dissolved, it is configured to a series of standard solution of various concentrations as high standard solution, is put in refrigerator stand-by.
(4) 8 mM L-cysteine solution are prepared: being accurately weighed 0.0078 g L-cysteine and be dissolved in 8 mL deionized waters
It shakes up and is allowed to be completely dissolved, a series of standard solution of various concentrations is configured to as high standard solution, be put in refrigerator stand-by.
Embodiment 3
The measurement of the ultra-violet absorption spectrum and fluorescence emission spectrum of metal-organic framework materials used in the present invention
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), the Tris-HCl of 400 μ L is slow
It rushes solution (pH=7.2,0.1 M) and is settled to 4 mL with deionized water, metal-organic framework materials is dense in final system solution
Degree is 10 mg L-1.Utilize the absorbance of ultraviolet-visible spectrophotometer detection architecture solution；Existed using sepectrophotofluorometer
Excitation wavelength is 282 nm, 5 nm of exciting slit, 5 nm of transmite slit, measures body under conditions of 560 V of Photomultiplier tube voltage
It is the fluorescent emission spectrogram of solution.As shown in figure 3,1 is uv absorption spectra figure, 2 be fluorescence emission spectrogram of compound.From Fig. 3
It can be seen that metal-organic framework materials have stronger UV absorption at 282 nm, therefore use 282 nm as excitation wavelength.When
When acting on system solution using the excitation wavelength of 282 nm, there is very strong fluorescence emission peak at 372 nm.
Embodiment 4
Based on metal-organic framework materials fluorometric investigation with the optimal test concentrations of determination
(1) suspension (the 100 mg L of 200 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
HCl buffer solution (pH=7.2,0.1 M) is settled to 4 mL with deionized water, is mixed after uniformly standing 40 min of reaction,
Utilize the fluorescence emission spectrum of fluorescent spectrophotometer assay reaction system.Successively it is separately added into 200 μ L metal organic framework materials
Suspension (the 100 mg L of material-1), the Tris-HCl buffer solution (pH=7.2,0.1 M) of 400 μ L, the lead chloride of 100 μ L
Solution (1.6 mM) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, utilizes sepectrophotofluorometer
Measure the fluorescence emission spectrum of reaction system.
(2) suspension (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
HCl buffer solution (pH=7.2,0.1 M) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, utilizes
The fluorescence emission spectrum of fluorescent spectrophotometer assay reaction system.Successively it is separately added into 400 μ L metal-organic framework materials
Suspension (100 mg L-1), the Tris-HCl buffer solution (pH=7.2,0.1 M) of 400 μ L, the chlorination lead solution of 100 μ L
(1.6 mM) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, utilizes fluorescent spectrophotometer assay
The fluorescence emission spectrum of reaction system.
(3) suspension (the 100 mg L of 800 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
HCl buffer solution (pH=7.2,0.1 M) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, utilizes
The fluorescence emission spectrum of fluorescent spectrophotometer assay reaction system.Successively it is separately added into 800 μ L metal-organic framework materials
Suspension (100 mg L-1), the Tris-HCl buffer solution (pH=7.2,0.1 M) of 400 μ L, the chlorination lead solution of 100 μ L
(1.6 mM) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, utilizes fluorescent spectrophotometer assay
The fluorescence emission spectrum of reaction system.
(4) suspension (the 100 mg L of 1200 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
HCl buffer solution (pH=7.2,0.1 M) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, utilizes
The fluorescence emission spectrum of fluorescent spectrophotometer assay reaction system.Successively it is separately added into 1200 μ L metal-organic framework materials
Suspension (100 mg L-1), the Tris-HCl buffer solution (pH=7.2,0.1 M) of 400 μ L, the lead chloride of 100 μ L is molten
Liquid (1.6 mM) is settled to 4 mL with deionized water, is uniformly mixed after standing 40 min of reaction, is surveyed using sepectrophotofluorometer
Determine the fluorescence emission spectrum of reaction system.
The fluorescence emission spectrum that metal-organic framework materials under various concentration are measured using the above method (it is molten to be added without lead chloride
Liquid) and the metal-organic framework materials solution of various concentration in be added equivalent chlorination lead solution after fluorescence emission spectrum,
The blank fluorescence intensity of metal-organic framework materials and the curve graph of fluorescent quenching intensity can be obtained.As shown in Figure 4, it can be seen that
It reaches fluorescence intensity increase to a certain degree as the increase of complex concentration its fluorescence intensity also increases as and tends to slowly, not
With in concentration complex solution there are under the conditions of the lead chloride of isoconcentration, fluorescent quenching efficiency with starting material concentrations increase and by
Gradually reduce.The corresponding starting material concentrations of two intersections of complex curve of final choice are that optimal test concentrations are (also optional according to the actual situation
Surrounding's concentration of a corresponding concentration is chosen friends as test concentrations), select concentration for 5-15 mg L in this application-1, preferably 8-11
mg L-1。
Embodiment 5
Determine system lead chloride to the best quenching time of metal-organic framework materials
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), the Tris-HCl of 400 μ L is slow
It rushes solution (pH=7.2,0.1 M), the chlorination lead solution (1.6 mM) of 100 μ L is settled to 4 mL with deionized water, is uniformly mixed
In the different time for standing 0-90 min, the fluorescence emission spectrum of fluorescent spectrophotometer assay reaction system is utilized.Such as attached drawing 5
It is shown, it can be seen that after chlorination lead solution is added over time, the fluorescence intensity of mixed system solution is in the short time
It inside reduces rapidly, then tends to slowly reduce within certain time, and in 40 min or so fluorescence intensity held stationary
(i.e. system quenching time is 30-50 min to state, best to quench the time as 40-45 min).Finally selected in fluorometric investigation
The fluorescence intensity of detection architecture after addition 40 min of chlorination lead solution, and object L-cysteine solution is added at this moment.
Embodiment 6
Determine that the fluorescence after metal organic framework complex material and lead chloride mixed solution system is added in L-cysteine restores
Time
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), the Tris-HCl of 400 μ L is slow
It rushes solution (pH=7.2,0.1 M), the chlorination lead solution (1.6 mM) of 100 μ L is settled to 4 mL with deionized water, is uniformly mixed
It stands after the solution system quenching time reaches 40 min, addition L-cysteine solution (1.2 mM), which is uniformly mixed, stands 0-60
In the different time of min, the fluorescence emission spectrum of fluorescence spectrophotometer measurement reaction system is utilized.As shown in Fig. 6, it can see
Out after L-cysteine solution is added over time, the fluorescence intensity of system solution enhances in a short time, and
It is held essentially constant that (i.e. the fluorescence recovery time of system is 20-40 min, preferably 25-30 in 30 min or so fluorescence intensity
min).30 min in metal-organic framework materials and lead chloride mixed solution system are added when L-cysteine solution in final choice
After carry out fluorometric investigation.
Embodiment 7
Determine quencher lead chloride dosage
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), the Tris-HCl of 400 μ L is slow
Solution (pH=7.2,0.1 M) is rushed, a series of chlorination lead solution of various concentrations (15-80 μM) spends ionized water and is settled to 4
ML is uniformly mixed and stands after the system solution reaction time reaches 40 min, has using fluorescent spectrophotometer assay in metal
There are the fluorescence intensities of mixed solution system emission spectrum under the lead chloride of various concentration, as system in machine framework material solution
The bias light spectrogram of fluorescent quenching.
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), the Tris-HCl of 400 μ L is slow
It rushes solution (pH=7.2,0.1 M), a series of chlorination lead solution of various concentrations (15-80 μM), is uniformly mixed and stands to system
After the solution reaction time reaches 40 min, L-cysteine solution (1.2 mM) is added with deionized water and is settled to 4 mL.To body
It is to be added using fluorescent spectrophotometer assay L-cysteine solution to mixed system solution after 30 min of solution reaction
The recovery that emission spectrum, as system fluorescence restore emits spectrogram.
The L-cysteine of same concentration can be obtained to there are the metals of various concentration lead chloride according to above-mentioned two test results
The fluorescence recovery strength of organic framework material mixed system solution.When chlorination lead concentration is 40-50 μM, to mixed solution body
The fluorescence recovery strength that 30 μM of L-cysteine solution is added in system is larger.When the chlorination lead concentration of addition is higher than 40 μM
When, L-cysteine is smaller to the fluorescence recovery strength of system and can lead to sensitivity decrease due to quencher excessive concentration.When
When the chlorination lead concentration of addition is lower than 40 μM, L-cysteine is smaller to the fluorescence recovery strength of system and system have it is higher
Fluorescence background value, can the biggish interference of detection architecture generation.Finally in fluorescent detection system, selection concentration is 35 μM of concentration
Lead chloride carry out subsequent experimental.
Embodiment 8
Determine the Optimal pH of entire reaction system
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), a series of difference pH of 400 μ L
The Tris-HCl buffer solution (0.1 M) of range (5.0-8.0) is settled to 4 mL with deionized water, is uniformly mixed and stands to system
It is as molten using the fluorescence emission spectrum of system solution under fluorescent spectrophotometer assay difference pH after 40 min of solution reaction
The emission spectrum Background of the blank of liquid system.
Successively it is separately added into suspension (the 100 mg L of 400 μ L metal-organic framework materials-1), a series of difference pH of 400 μ L
The chlorination lead solution (1.6 mM) of the Tris-HCl buffer solution (0.1 M) of range (5.0-8.0), 100 μ L is fixed with deionized water
Hold to 4 mL, is uniformly mixed and stands after system solution reacts 40 min, utilize fluorescent spectrophotometer assay difference pH lower body
It is the launching light spectrogram of the fluorescent quenching of solution, the as fluorescent quenching Background of mixed solution system.
Successively it is separately added into 400 μ L metal-organic framework materials suspension (100 mg L-1), a series of difference pH models of 400 μ L
The Tris-HCl buffer solution (0.1 M) of (5.0-8.0) is enclosed, the chlorination lead solution (1.6 mM) of 100 μ L is anti-to system solution
After answering 40 min, L-cysteine solution (1.2 mM) is added with deionized water and is settled to 4 mL, to solution system reaction 30
After min, restore launching light spectrogram using the fluorescence of system solution under fluorescent spectrophotometer assay difference pH.
A series of fluorescent quenching effect of the metal-organic framework materials at difference pH can be obtained according to above-mentioned three test results
The curve graph of rate and fluorescence recovery strength, as shown in Figure 8.When the pH of Tris-HCl buffer solution (0.1 M) is (excellent in 7.0-7.6
Select between 7.2-7.4) when, the fluorescence recovery strength that L-cysteine is added into mixed system solution is maximum.When pH is higher than 7.2
When, the fluorescence recovery strength of system and the fluorescent quenching efficiency of system solution are all gradually dropped as pH increases L-cysteine
It is low, cause system to have higher fluorescence background value, larger interference can be generated for system detection.When pH is lower than 7.2, with pH
L-cysteine of successively decreasing the fluorescence recovery strength of system is gradually reduced, the fluorescent quenching efficiency of system gradually increases finally
Tend to be steady state.In fluorescence detection, since higher fluorescent quenching efficiency can reduce the spirit of detection architecture when pH value is smaller
Sensitivity comprehensively considers different pH to the fluorescence recovery strength of system and the influence of fluorescent quenching efficiency, final choice pH=7.2
Optimal test condition as detection architecture.
Embodiment 9
L-cysteine is detected using the mixed system of metal-organic framework materials and lead chloride
(1) suspension (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
The chlorination lead solution (1.6 mM) of HCl buffer solution (pH=7.2,0.1 M), 100 μ L is settled to 4 mL with deionized water, mixes
After conjunction uniformly stands best 40 min of quenching time to be achieved, the fluorescent emission of fluorescent spectrophotometer assay reaction system is utilized
Spectrum, bias light spectrogram of this emission spectrum as fluorescent quenching.
(2) suspension (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
It is to be achieved best to be uniformly mixed standing for HCl buffer solution (pH=7.2,0.1 M), the chlorination lead solution (1.6 mM) of 100 μ L
After quenching 40 min of time, a series of L-cysteine solution of various concentrations (0.25-40 μM) is added, system solution is used
Deionized water is settled to 4 mL.After 30 min of system solution reaction to be mixed stablize, reacted using fluorescent spectrophotometer assay
The fluorescence intensity of the fluorescence emission spectrum of system, the bias light spectrogram of the fluorescence intensity and fluorescent quenching of this fluorescence emission spectrum is poor
It is worth the fluorescence recovery strength as emission spectrum, by the fluorescence recovery strength of fluorescence emission spectrum and L-cysteine solution is added
Concentration carry out linear fit.As shown in attached drawing 9 and 10, with the increase of L-cysteine concentration, the fluorescence of reaction system is strong
Degree recovery value is gradually increased, and is within the scope of 0.25-40 μM in L-cysteine concentration, L-cysteine is dense in reaction system
Degree is in good linear relationship with fluorescence recovery strength, and linear equation is △ I=14.199C+29.32.It is above-mentioned
The analysis characteristic quantity of method is as shown in the table, illustrates that this method has the wider range of linearity and lower detection limit.
The analysis characteristic quantity of 4 this method of table
Embodiment 10
Based on metal-organic framework materials as fluorescence probe to the selective enumeration method of L-cysteine
(1) suspension (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
The chlorination lead solution (1.6 mM) of HCl buffer solution (pH=7.2,0.1 M), 100 μ L is settled to 4 mL with deionized water, mixes
After conjunction uniformly stands best 40 min of quenching time to be achieved, the fluorescent emission of fluorescent spectrophotometer assay reaction system is utilized
Spectrum, bias light spectrogram of this emission spectrum as fluorescent quenching.
(2) suspension (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), the Tris- of 400 μ L
It is to be achieved best to be uniformly mixed standing for HCl buffer solution (pH=7.2,0.1 M), the chlorination lead solution (1.6 mM) of 100 μ L
After quenching 40 min of time, it is separately added into a series of equal L-cysteine of 100 concentration of μ L, glutathione, glutamic acid, sweet
Propylhomoserin, dopamine, arginine, histidine, leucine, lysine, threonine, valine, methionine standard solution (0.8
MM), system solution is settled to 4 mL with deionized water.It is uniformly mixed 30 min of standing system solution reaction to be mixed and reaches steady
After determining state, using the fluorescence emission spectrum of fluorescent spectrophotometer assay reaction system, the fluorescence of this fluorescence emission spectrum is strong
The fluorescence intensity ratio of degree and the bias light spectrogram of fluorescent quenching alternatively property reference standard.The data obtained result is depicted as
Histogram has investigated influence of the different biological micromolecules to fluorescence probe fluorescence intensity as shown in Fig. 11.
The results show that the fluorescence intensity generation that just will lead to system after adding L-cysteine only in mixed system solution is bright
Aobvious enhancing, and other biological small molecule shows that this analysis method has good selectivity, this is glimmering almost without apparent response
Light probe detection architecture is able to carry out specific recognition to L-cysteine.
Claims (3)
1. a kind of method based on calcium-metal-organic framework materials as fluorescence probe detection L-cysteine, which is characterized in that
It carries out in accordance with the following steps:
(1) preparation of Standard Stock solutions: the metal-organic framework materials that quality is 0.0060 g are weighed and are dissolved in 60 mL deionizations
It is shaken up in water and is allowed to be completely dissolved；Weighing quality is that 0.7780 g trihydroxy aminomethane-hydrochloric acid (Tris-HCl) is dissolved in 50 mL
Deionized water in shake up and be allowed to be completely dissolved；It weighs 0.0178 g lead chloride analytical reagent and is dissolved in 8 mL deionized waters and shake up
It is allowed to be completely dissolved；It weighs 0.0078 g L-cysteine and is dissolved in shaking up in 8 mL deionized waters and be allowed to be completely dissolved；
(2) aaerosol solution (the 100 mg L of 400 μ L metal-organic framework materials are successively separately added into-1), standard Tris-HCl is slow
It rushes solution (pH=7.2,0.1 M) and 100 μ L standard chlorination lead solutions (1.6 mM) and is settled to 4 mL with deionized water, mix
It uniformly stands lead to be chlorinated and metal-organic framework materials interaction reaches stable state, cause MOFs material to generate fluorescence sudden
Go out signal, and detection architecture is in fluorescence intensity positioned at the fluorescence closed state compared with low background, is remembered using sepectrophotofluorometer
Record fluorescence emission spectrum；
(3) solution to be measured containing L-cysteine is added into the detection architecture solution of step (2), uniformly mixing, which is stood, makes L-
After cysteine and lead chloride interaction are stablized, detection architecture is set to be restored in the fluorescence intensity compared with low background, benefit
Fluorescence emission spectrum is recorded with sepectrophotofluorometer；Pass through the changing value of fluorescence emission spectral intensity recorded twice and fitting
Linear equation guidance obtain the concentration of L-cysteine in solution to be measured.
2. the method for detection L-cysteine described in claims 1, it is characterised in that the linear equation of fitting be △ I=
14.199C+29.32 0.25-40 μM of the range of linearity, minimum detectability 91 nM, R2Value is 0.98043.
3. the method for detection L-cysteine described in claims 1, it is characterised in that metal-organic framework materials are a kind of
Based on (1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid)-Ca (NO3)2Hypotoxicity porous coordination polymer material, should
Material crystal structure belongs to monoclinic system, C2/cSpace group, chemical general formula are as follows: { [Ca1.5(HL1)(DMF)2] DMF, with Ca2 +Centered on metal ion, HL is (1,1':4', 1 "-terphenyl -3,3 ", 5,5 "-tetrabasic carboxylic acid) as organic bridge ligand,
Organic ligand structure are as follows:
。
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